The reference window for reduced perturbation of the reference wave in electrical biasing off-axis electron holography.

The perturbation of the reference wave due to electric stray fields represents a major challenge in quantitative electron holographic investigations. By introducing a focused-ion-beam-milled rectangular hole, the reference window, in an area of nearly constant electrostatic potential of the sample, this perturbation can be significantly reduced. The edge of the window forms a closed conducting loop, acting similarly to a Faraday cage, shielding the influence of the stray field on the reference wave to some extent. In this work, the shielding effect of the reference window is systematically investigated by comparing electron holograms of an electrically biased coplanar capacitor, as a well-known reference sample, with finite element simulations. It is shown that the introduction of the reference window into electrical biasing samples both suppresses unknown lateral phase distortions substantially and in addition improves the agreement of the experimentally observed phase slope with that expected by simulation significantly, particularly for small object-reference wave distances. Consequently, a slight adjustment of the sample geometry results in an improved reproducibility of electron holographic electrical biasing experiments, which is a significant step towards quantitative evaluation.

Laser-induced tuning of crystallization in tetracene thin films.

This study explores how laser light affects the morphology of tetracene films, and it presents novel strategies for improving the creation of thin films used in (opto-)electronic devices. We demonstrate that laser light (532 nm, 1.1 W mm-2), applied during tetracene deposition, not only increases grain size but also induces photoalignment. The observed effects arise from enhanced molecular diffusion, resulting from energy transferred by light to the molecules after adsorption, but not from heating the substrate surface underneath. We observe that linearly polarized light promotes photoalignment, while increased crystallite sizes occurs with both linear and circular polarizations. We propose an Ostwald ripening process facilitated by laser illumination, where smaller crystallites get optically heated and dissolve, allowing molecules to surmount step-edge barriers and assemble into larger crystallites. Importantly, the crystallite sizes achieved with laser illumination surpass those attainable by substrate heating alone. The study demonstrates that laser illumination acts as a promising new parameter for controlling thin film properties and is distinct from growth control via substrate temperature and growth rate. Light control also includes the ability for lateral patterning, with implications for the future of molecular materials and their manufacturing technologies.

Phase Segregation Mechanisms in Mixed-Halide CsPb(BrxI1-x)3 Nanocrystals in Dependence of Their Sizes and Their Initial [Br]:[I] Ratios.

Phase segregation in inorganic CsPb(BrxI1-x)3 nanoparticles (NPs) exhibiting originally a homogeneous [Br]:[I] mixture was investigated by means of in situ transmission electron microscopy (TEM) and evaluated by using multivariate analyses. The colloidal synthesis of the NPs offers good control of the halide ratios on the nanoscale. The spatially resolved TEM investigations were correlated with integral photoluminescence measurements. By this approach, the halide-segregation processes and their spatial distributions can be described as being governed by the interaction of three partial processes: electron- and photon-irradiation-induced iodide oxidation, local differences in band gap energy, and intrinsic lattice strain. Since the oxidation can be induced by both electron-beam and light irradiation, both irradiation types can induce phase segregation in CsPb(BrxI1-x)3 compounds. This makes in situ TEM a valuable tool to monitor phase transformation in corresponding NPs and thin films on the sub-nm scale.

Atomic-Resolution Mapping of Localized Phonon Modes at Grain Boundaries.

Phonon scattering at grain boundaries (GBs) is significant in controlling the nanoscale device thermal conductivity. However, GBs could also act as waveguides for selected modes. To measure localized GB phonon modes, milli-electron volt (meV) energy resolution is needed with subnanometer spatial resolution. Using monochromated electron energy loss spectroscopy (EELS) in the scanning transmission electron microscope (STEM) we have mapped the 60 meV optic mode across GBs in silicon at atomic resolution and compared it to calculated phonon densities of states (DOS). The intensity is strongly reduced at GBs characterized by the presence of 5- and 7-fold rings where bond angles differ from the bulk. The excellent agreement between theory and experiment strongly supports the existence of localized phonon modes and thus of GBs acting as waveguides.

On the non-bonding valence band and the electronic properties of poly(triazine imide), a graphitic carbon nitride.

Graphitic carbon nitrides are covalently-bonded, layered, and crystalline semiconductors with high thermal and oxidative stability. These properties make graphitic carbon nitrides potentially useful in overcoming the limitations of 0D molecular and 1D polymer semiconductors. In this contribution, we study structural, vibrational, electronic and transport properties of nano-crystals of poly(triazine-imide) (PTI) derivatives with intercalated Li- and Br-ions and without intercalates. Intercalation-free poly(triazine-imide) (PTI-IF) is corrugated or AB stacked and partially exfoliated. We find that the lowest energy electronic transition in PTI is forbidden due to a non-bonding uppermost valence band and that its electroluminescence from the π-π* transition is quenched which severely limits their use as emission layer in electroluminescent devices. THz conductivity in nano-crystalline PTI is up to eight orders of magnitude higher than the macroscopic conductivity of PTI films. We find that the charge carrier density of PTI nano-crystals is among the highest of all known intrinsic semiconductors, however, macroscopic charge transport in films of PTI is limited by disorder at crystal-crystal interfaces. Future device applications of PTI will benefit most from single crystal devices that make use of electron transport in the lowest, π-like conduction band.

Growth of κ-([Al,In]xGa1-x)2O3 Quantum Wells and Their Potential for Quantum-Well Infrared Photodetectors.

The wide band gap semiconductor κ-Ga2O3 and its aluminum and indium alloys have been proposed as promising materials for many applications. One of them is the use of inter-sub-band transitions in quantum-well (QW) systems for infrared detectors. Our simulations show that the detection wavelength range of nowadays state of the art GaAs/AlxGa1-xAs quantum-well infrared photodetectors (QWIPs) could be substantially excelled with about 1-100 µm using κ-([Al,In]xGa1-x)2O3, while at the same time being transparent to visible light and therefore insensitive to photon noise due to its wide band gap, demonstrating the application potential of this material system. Our simulations further show that the QWIPs efficiency critically depends on the QW thickness, making a precise control over the thickness during growth and a reliable thickness determination essential. We demonstrate that pulsed laser deposition yields the needed accuracy, by analyzing a series of (InxGa1-x)2O3 QWs with (AlyGa1-y)2O3 barriers with high-resolution X-ray diffraction, X-ray photoelectron spectroscopy (XPS) depth profiling, and transmission electron microscopy (TEM). While the superlattice fringes of high-resolution X-ray diffraction only yield an average combined thickness of the QWs and the barrier and X-ray spectroscopy depth profiling requires elaborated modeling of the XPS signal to accurately determine the thickness of such QWs, TEM is the method of choice when it comes to the determination of QW thicknesses.

Deep reinforcement learning for data-driven adaptive scanning in ptychography.

We present a method that lowers the dose required for an electron ptychographic reconstruction by adaptively scanning the specimen, thereby providing the required spatial information redundancy in the regions of highest importance. The proposed method is built upon a deep learning model that is trained by reinforcement learning, using prior knowledge of the specimen structure from training data sets. We show that using adaptive scanning for electron ptychography outperforms alternative low-dose ptychography experiments in terms of reconstruction resolution and quality.

Solving the crystallographic phase problem using dynamical scattering in electron diffraction.

Solving crystal structures from kinematical X-ray or electron diffraction patterns of single crystals requires many more diffracted beams to be recorded than there are atoms in the structure, since the phases of the structure factors can only be retrieved from such data if the atoms can be resolved as sharply peaked objects. Here a method is presented by which the fact that multiple scattering encodes structure factor phases in the diffracted intensities is being used for solving the crystallographic phase problem. The retrieval of both amplitudes and phases of electron structure factors from diffraction patterns recorded with varying angle of incidence will be demonstrated. No assumption about the scattering potential itself is being made. In particular, the resolution in the diffraction data does not need to be sufficient to resolve atoms, making this method potentially interesting for electron crystallography of 2-dimensional protein crystals and other beam-sensitive complex structures.

Direct Visualization of Subnanometer Variations in the Excitonic Spectra of 2D/3D Semiconductor/Metal Heterostructures.

The integration of metallic contacts with two-dimensional (2D) semiconductors is routinely required for the fabrication of nanoscale devices. However, nanometer-scale variations in the 2D/metal interface can drastically alter the local optoelectronic properties. Here, we map local excitonic changes of the 2D semiconductor MoS2 in contact with Au. We utilize a suspended and epitaxially grown 2D/metal platform that allows correlated electron energy-loss spectroscopy (EELS) and angle resolved photoelectron spectroscopy (nanoARPES) mapping. Spatial localization of MoS2 excitons uncovers an additional EELS peak related to the MoS2/Au interface. NanoARPES measurements indicate that Au-S hybridization decreases substantially with distance from the 2D/metal interface, suggesting that the observed EELS peak arises due to dielectric screening of the excitonic Coulomb interaction. Our results suggest that increasing the van der Waals distance could optimize excitonic spectra of mixed-dimensional 2D/3D interfaces and highlight opportunities for Coulomb engineering of exciton energies by the local dielectric environment or moiré engineering.

Synergistic use of gradient flipping and phase prediction for inline electron holography.

Inline holography in the transmission electron microscope is a versatile technique which provides real-space phase information that can be used for the correction of imaging aberrations, as well as for measuring electric and magnetic fields and strain distributions. It is able to recover high-spatial-frequency contributions of the phase effectively but suffers from the weak transfer of low-spatial-frequency information, as well as from incoherent scattering. Here, we combine gradient flipping and phase prediction in an iterative flux-preserving focal series reconstruction algorithm with incoherent background subtraction that gives extensive access to the missing low spatial frequencies. A procedure for optimizing the reconstruction parameters is presented, and results from Fe-filled C nanospheres, and MgO cubes are compared with phase images obtained using off-axis holography.

Poly(ionic liquid) Nanovesicle-Templated Carbon Nanocapsules Functionalized with Uniform Iron Nitride Nanoparticles as Catalytic Sulfur Host for Li-S Batteries.

Poly(ionic liquid)s (PIL) are common precursors for heteroatom-doped carbon materials. Despite a relatively higher carbonization yield, the PIL-to-carbon conversion process faces challenges in preserving morphological and structural motifs on the nanoscale. Assisted by a thin polydopamine coating route and ion exchange, imidazolium-based PIL nanovesicles were successfully applied in morphology-maintaining carbonization to prepare carbon composite nanocapsules. Extending this strategy further to their composites, we demonstrate the synthesis of carbon composite nanocapsules functionalized with iron nitride nanoparticles of an ultrafine, uniform size of 3-5 nm (termed "FexN@C"). Due to its unique nanostructure, the sulfur-loaded FexN@C electrode was tested to efficiently mitigate the notorious shuttle effect of lithium polysulfides (LiPSs) in Li-S batteries. The cavity of the carbon nanocapsules was spotted to better the loading content of sulfur. The well-dispersed iron nitride nanoparticles effectively catalyze the conversion of LiPSs to Li2S, owing to their high electronic conductivity and strong binding power to LiPSs. Benefiting from this well-crafted composite nanostructure, the constructed FexN@C/S cathode demonstrated a fairly high discharge capacity of 1085 mAh g-1 at 0.5 C initially, and a remaining value of 930 mAh g-1 after 200 cycles. In addition, it exhibits an excellent rate capability with a high initial discharge capacity of 889.8 mAh g-1 at 2 C. This facile PIL-to-nanocarbon synthetic approach is applicable for the exquisite design of complex hybrid carbon nanostructures with potential use in electrochemical energy storage and conversion.

High-Resolution Mapping of Strain Partitioning and Relaxation in InGaN/GaN Nanowire Heterostructures.

Growing an Inx Ga1- x N/GaN (InGaN/GaN) multi-quantum well (MQW) heterostructure in nanowire (NW) form is expected to overcome limitations inherent in light-emitting diodes (LEDs) based on the conventional planar heterostructure. The epitaxial strain induced in InGaN/GaN MQW heterostructure can be relaxed through the sidewalls of NW, which is beneficial to LEDs because a much larger misfit strain with higher indium concentration can be accommodated with reduced piezoelectric polarization fields. The strain relaxation, however, renders highly complex strain distribution within the NW heterostructure. Here the authors show that complementary strain mapping using scanning transmission electron microscopy and dark-field inline holography can comprehend the strain distribution within the axial In0.3 Ga0.7 N/GaN MQW heterostructure embedded in GaN NW by providing the strain maps which can cover the entire NW and fine details near the sidewalls. With the quantitative evaluation by 3D finite element modelling, it is confirmed that the observed complex strain distribution is induced by the strain relaxation leading to the strain partitioning between InGaN quantum disk, GaN quantum well, and the surrounding epitaxial GaN shell. The authors further show that the strain maps provide the strain tensor components which are crucial for accurate assessment of the strain-induced piezoelectric fields in NW LEDs.

Large Area Ultrathin InN and Tin Doped InN Nanosheets Featuring 2D Electron Gases.

Indium nitride (InN) has been of significant interest for creating and studying two-dimensional electron gases (2DEG). Herein we demonstrate the formation of 2DEGs in ultrathin doped and undoped 2D InN nanosheets featuring high carrier mobilities at room temperature. The synthesis is carried out via a two-step liquid metal-based printing method followed by a microwave plasma-enhanced nitridation reaction. Ultrathin InN nanosheets with a thickness of ∼2 ± 0.2 nm were isolated over large areas with lateral dimensions exceeding centimeter scale. Room temperature Hall effect measurements reveal carrier mobilities of ∼216 and ∼148 cm2 V-1 s-1 for undoped and doped InN, respectively. Further analysis suggests the presence of defined quantized states in these ultrathin nitride nanosheets that can be attributed to a 2D electron gas forming due to strong out-of-plane confinement. Overall, the combination of electronic and plasmonic features in undoped and doped ultrathin 2D InN holds promise for creating advanced optoelectronic devices and functional 2D heterostructures.

FAIR data enabling new horizons for materials research.

The prosperity and lifestyle of our society are very much governed by achievements in condensed matter physics, chemistry and materials science, because new products for sectors such as energy, the environment, health, mobility and information technology (IT) rely largely on improved or even new materials. Examples include solid-state lighting, touchscreens, batteries, implants, drug delivery and many more. The enormous amount of research data produced every day in these fields represents a gold mine of the twenty-first century. This gold mine is, however, of little value if these data are not comprehensively characterized and made available. How can we refine this feedstock; that is, turn data into knowledge and value? For this, a FAIR (findable, accessible, interoperable and reusable) data infrastructure is a must. Only then can data be readily shared and explored using data analytics and artificial intelligence (AI) methods. Making data 'findable and AI ready' (a forward-looking interpretation of the acronym) will change the way in which science is carried out today. In this Perspective, we discuss how we can prepare to make this happen for the field of materials science.

High-k 2D Sb2O3 Made Using a Substrate-Independent and Low-Temperature Liquid-Metal-Based Process.

High dielectric constant (high-k) ultrathin films are required as insulating gate materials. The well-known high-k dielectrics, including HfO2, ZrO2, and SrTiO3, feature three-dimensional lattice structures and are thus not easily obtained in the form of distinct ultrathin sheets. Therefore, their deposition as ultrathin layers still imposes challenges for electronic industries. Consequently, new high-k nanomaterials with k in the range of 40 to 100 and a band gap exceeding 4 eV are highly sought after. Antimony oxide nanosheets appear as a potential candidate that could fulfill these characteristics. Here, we report on the stoichiometric cubic polymorph of 2D antimony oxide (Sb2O3) as an ideal high-k dielectric sheet that can be synthesized via a low-temperature, substrate-independent, and silicon-industry-compatible liquid metal synthesis technique. A bismuth-antimony alloy was produced during the growth process. Preferential oxidation caused the surface of the melt to be dominated by α-Sb2O3. This ultrathin α-Sb2O3 was then deposited onto desired surfaces via a liquid metal print transfer. A tunable sheet thickness between ∼1.5 and ∼3 nm was achieved, while the lateral dimensions were within the millimeter range. The obtained α-Sb2O3 exhibited high crystallinity and a wide band gap of ∼4.4 eV. The relative permittivity assessment revealed a maximum k of 84, while a breakdown electric field of ∼10 MV/cm was observed. The isolated 2D α-Sb2O3 nanosheets were utilized in top-gated field-effect transistors that featured low leakage currents, highlighting that the obtained material is a promising gate oxide for conventional and van der Waals heterostructure-based electronics.

Quantifying the data quality of focal series for inline electron holography.

Inline electron holography, the recovery of amplitude and phase of an electron wave function having passed through a thin specimen from a focal series recorded in a transmission electron microscope is being applied in many labs worldwide. At medium range magnification (i.e. typically ≥0.8 nm where the lattice of small unit cell crystals such as silicon is not resolved), where the defocus needs to be varied over a rather large range of several hundred nm or even µm, the retrieval of low spatial frequency information is severely affected by the choice of experimental parameters as well as the way of data normalization. Methods to quantitatively analyze the reliability of phase maps obtained by inline electron holography are presented, and data recorded and processed in different ways are compared. While, even under optimized conditions, the phase reconstructed from an experimental focal series still lacks very low spatial frequency components, regularization schemes exist and are demonstrated to effectively hide artifacts associated with this lack of information.

Analysis of Local Charges at Hetero-interfaces by Electron Holography - A Comparative Study of Different Techniques.

Interface charges confined within a few nanometers of hetero-interface can be characterized by measuring the phase shift of the transmitted beam using different electron holography techniques. However, reliable measurement of the electrostatic potential arising from the interface charges is challenging as the mean inner potential difference (ΔV0) between two adjoining materials as well as local variation of the sample thickness affect the phase shift. In the present study, we show how electron holography can be used to characterize the confined charges at an oxide hetero-interface and evaluate the applicability of different techniques for this purpose. The model system chosen for this study is a LaAlO3/SrTiO3 (LAO/STO) (111) hetero-interface featuring a two-dimensional electron gas (2DEG), where the ΔV0 between LAO and STO is about 2 eV, which is unignorably large and dominates the net potential variation across the interface. For transmission electron microscopy specimens prepared by focused ion beam we applied three different variants of electron holography techniques: off-axis, inline and hybrid electron holography; and compare the results obtained by these approaches in terms of the information transfer in the spatial frequency domain, and the signal-to-noise ratio of the electric field and charge density maps. To correctly assess the information pertinent to the interface-confined charges, we calculate the electrostatic potential and electric field distribution based on a charge model with taking account of the ΔV0 between LAO and STO and compared the calculated profiles with the experimental results after calibrating the local thickness variation across the LAO/STO interface. The results show that hybrid electron holography recovers the information across a wide range of spatial frequencies, and as a result, delivers the most reliable charge density information, albeit convoluted with the unavoidable effects arising from ΔV0.